Adsorption isotherms for neutral organic compounds-A hierarchy in modelling: Part III

A simple three-state model permitting two different configurational states for the solvent, together with one for the organic adsorbate, is analysed to derive the adsorption isotherm. The implications of this model regarding pseudo-two-state and pseudo-Frumkin adsorption isotherms are indicated. A critique of the earlier theory of Bockris, Devanathan and Müller is presented in brief.

Adsorption isitherms for neutral organic compounds-A hierarchy in modelling: Part IV. Charge of maximum adsorption-Statistical mechanical basis

The charge at which adsorption of orgamc compounds attains a maximum ( \sigma MAX M) at an electrochenucal interface is analysed using several multi-state models in a hierarchical manner The analysis is based on statistical mechamcal results for the following models (A) two-state site parity, (B) two-state muhl-slte, and (C) three-state site parity The coulombic interactions due to permanent and reduced dipole effects (using mean field approximation), electrostatic field effects and specific substrate interactions have been taken into account. The simplest model in the hierarchy (two-state site parity) yields the exphcit dependence of ( \sigma MAX M) on the permanent dipole moment, polarizability of the solvent and the adsorbate, lattice spacing, effective coordination number, etc Other models in the baerarchy bring to hght the influence of the solvent structure and the role of substrate interactions, etc As a result of this approach, the "composition" of oM.x m terms of the fundamental molecular constants becomes clear. With a view to use these molecular results to maxamum advantage, the derived results for ( \sigma MAX M) have been converted into those involving experimentally observable parameters lake Co, C 1, E N, etc Wherever possible, some of the earlier phenomenologlcal relations reported for ( \sigma MAX M), notably by Parsons, Damaskm and Frumkln, and Trasattl, are shown to have a certain molecular basis, vlz a simple two-state sate panty model.As a corollary to the hxerarcbacal modelling, \sigma MAX M and the potential corresponding to at (Emax) are shown to be constants independent of 0max or Corg for all models The lmphcatlon of our analysis f o r OmMa x with respect to that predicted by the generalized surface layer equation (which postulates Om~ and Ema x varlaUon with 0) is discussed in detail Finally we discuss an passing o M. and the electrosorptlon valency an this context.

Adsorption isotherms for neutral organic compounds - A hierarchy in modelling: Part V. Models for the inner layer potential difference in the presence of dipolar adsorption

The relations for the inner layer potential &fference (E) in the presence of adsorbed orgamc molecules are derived for three hterarchlcal models, m terms of molecular constants like permanent &pole moments, polarlzablhtles, etc It is shown how the experimentally observed patterns of the E vs 0 plots (hnear m all ranges of $\sigma^M$, non-linear in one or both regions of o M, etc ) can be understood in a serm-quantltatlve manner from the simplest model in our hierarchy, viz the two-state site panty version Two-state multi-site and three-state (sxte panty) models are also analysed and the slope (3E/80),,M tabulated for these also The results for the Esm-Markov effect are denved for all the models and compared with the earlier result of Parsons. A comparison with the GSL phenomenologlcal equation is presented and its molecular basis, as well as the hmltatlons, is analysed. In partxcular, two-state multa-slte and three-state (site panty) models yield E-o M relations that are more general than the "umfied" GSL equation The posslblhty of vaewlng the compact layer as a "composite medium" with an "effective dlelectnc constant" and obtaimng novel phenomenological descnptions IS also indicated.

Reversible Water Intercalation Accompanied by Coordination and Color Changes in a Layered Metal-Organic Framework

A new two-dimensional 3d-4f mixed-metal mixed dicarboxylate (homocyclic and heterocyclic) of the formula [Gd2(H2O)2Ni(H2O)2(1,2-bdc)2(2,5-pydc)2] 3 8H2O (1; 1,2-H2bdc = 1,2-benzenedicarboxylic acid and 2,5-H2pydc = 2,5- pyridinedicarboxylic acid) has been prepared by employing the hydrothermal method. The structure has infinite onedimensional-Gd-O-Gd- chains formed by the edge-shared GdO9 polyhedral units, resulting exclusively from the connectivity between the Gd3+ ions and the 1,2-bdc units. The chains are connected by the [Ni(H2O)2(2,5-pydc)2]2- metalloligand, forming the two-dimensional layer arrangements. The stacking of the layers creates hydrophilic and hydrophobic spaces in the interlamellar region. A one-dimensional water ladder structure, formed by the extraframework water molecules, occupies the hydrophilic region while the benzene ring of 1,2-bdc occupies the hydrophobic region. To the best of our knowledge, the present compound represents the first example of a 3d-4f mixed-metal carboxylate in which two different aromatic dicarboxylate anions act as the linkers. The stabilization energies of the water clusters have been evaluated using density functional theory calculations. The water molecules in 1 are fully reversible accompanied by a change in color (greenish blue to brown) and coordination around Ni2+ ions (octahedral to distorted tetrahedral).

Charge transfer complexes of crown ethers with neutral organic gyama-acceptor, 2-dicyanoethylene 1,3-indane dione

The interaction of benzo-15-crown-5, dibenzo-18-crown-6 and dibenzo-24-crown-8 with 2-dicyanoethylene 1,3-indane dione in CH2Cl2 has been described in terms of the formation of 1 : 1 molecular complexes. The magnitude of association constants and thermodynamic parameters indicate cooperative interactions of oxygens with the acceptors. The 1H and 13C NMR spectra of the complexes show that gyama-gyama interactions are a major source of ground state stabilization in these complexes.

Understanding solvent effects on structure and reactivity of organic intermediates: a Raman study

The effect of solvent on chemical reactivity has generally been explained on the basis of the dielectric constant and viscosity. However a number of spectroscopic studies, including UV-VIS, IR and Raman, has led to numerous empirical parameters to define solvent effect based on either solvating ability or polarity scale. These parameters include solvent polarizability, dipolarity, Lewis acidity and Lewis basicity, E-T(30), pi*, alpha, beta etc. However, from a structural point of view, we can separate solvation as static and dynamic processes. The static solvation basically relates to stabilization of the molecular structure by the solvent to attain the equilibrium structure, both in the intermediate and ground state. Dynamic solvation relates to solvent reorganization-induced dynamics prior to the structural reorganization to reach the equilibrium state. In this paper, we present (a) structural distortions induced by the solvent due to preferential solvation of the triplet excited state, and (b) the importance of dynamic solvation induced by vibronic coupling (pseudo-Jahn-Teller coupling). The examples include the effect of solvent on structure and reactivity of excited states of 2,2,2-trifluoroacetophenone (TFA). Based on the comparison of time resolved resonance Raman (TR3) data of TFA and other substituted acetophenone systems, it was found that change in solvent polarity indeed results in electronic state switching and structural changes in the excited state, which explains the trend in reactivity. Further, a TR3 study of fluoranil (FA) in the triplet excited state in solvents of varying polarities indicates that the structure of FA in the triplet excited state is determined by vibronic coupling effects and thus distorted structure. These experimental results have been well supported by density functional theoretical computational studies.

Thermal Conductivities of Organic Liquids-A New Correlation.

A new equation for predicting the thermal conductivities of organic liquids using dimension-less analysis is given. The equation (Equation Presented) correlates 51 different liquids tested within 11% average error and 17% standard deviation. A comparison of the proposed equation with the available correlations and its application to some industrially important liquids show that this equation can be safely used to calculate the thermal conductivities at 20°C. and 1 atm. pressure for organic liquids of known molecular weight. Cp and ΔHv - the only two parameters for which experimental values must be known for making use of this equation - can be calculated using other well known correlations. The proposed equation is not applicable to inorganic liquids.

Substituent effects on the addition of alcohols and anilines to organic isothiocyanates

The addition reactions of alcohols, ROH (R = CH3, C2H5 n-C3H7, i-C3H7 and t-C4H9), to p-bromophenylisothiocyanate show that the rates decrease in the order, CH3OH> C2H5OH> n-C3H7OH> i-C3H7OH> t-C4H9OH, although the basicities of the alcohols vary in the reverse order. The results indicate the greater importance of steric factors as compared with polar factors. Evidence is also presented for the formation of a complex between the isothiocyanate and the alcohol in the first stage of the addition reaction. In the addition of aniline to substituted phenylisothiocyanates the rate data give a satisfactory linear correlation with Hammett σ constants and the results clearly show that electron-withdrawing groups favour the addition reaction. The addition of aniline to alkyl isothiocyanates have been studied in order to find out the nature of alkyl group interaction in these derivatives. Kinetic studies on the addition of substituted anilines to phenylisothiocyanate show that the rate of reaction increases with the electron-donating ability of the substituents on the aniline as also the basicity of the aniline.

A formate bridged Ni(II) sheet and its 3D analogue in presence of a linear organic linker: Synthesis, crystal structure and magnetic properties

Reaction of formamide with Ni(NO3)(2)center dot 6H(2)O under hydrothermal condition in a mixture of MeOH/H2O forms a two-dimensional formate bridged sheet Ni(HCOO)(2)(MeOH)(2) (1). X-ray structure analysis reveals the conversion of formamide to formate which acts as a bridging ligand in complex 1 where the axial sites of Ni(II) are occupied by methanol used as a solvent. An analogous reaction in presence of 4,4'-bipyridyl (4,4'-bipy) yielded a three-dimensional structure Ni(HCOO)(2)(4,4'-bpy) (2). DC magnetic measurements as a function of temperature and field established the presence of spontaneous magnetization with T-c (Curie temperature) = 17 and 20.8 K in 1 and 2, respectively, which can be attributed due to spin-canting. DFT calculations were performed to corroborate the magnetic results of 1 and 2. (C) 2010 Elsevier Ltd. All rights reserved.

Self-assembled composite nano-materials exploiting a thermo reversible n-acene fibrillar scaffold and organic-capped ZnO nanoparticles

An organic-inorganic composite material is obtained by self-assembly of 2,3-didecyloxy-anthracene (DDOA), an organogelator of butanol, and organic-capped ZnO nanoparticles (NPs). The ligand 3, 2,3-di(6-oxy-n-hexanoic acid)-anthracene, designed to cap ZnO and interact with the DDOA nanofibers by structural similarity, improves the dispersion of the NPs into the organogel. The composite material displays mechanical properties similar to those of the pristine DDOA organogel, but gelates at a lower critical concentration and emits significantly less, even in the presence of very small amounts of ZnO NPs. The ligand 3 could also act as a relay to promote the photo-induced quenching process.

Factors contributing to phantom bonds in inorganic molecules: Interpretations and predictions

The validity of various qualitative proposals for interpreting and predicting the existence of short contacts between formally non-bonded atoms, as in cyclodisiloxane and related inorganic ring systems, is critically evaluated. The models range from simple considerations of geometric constraints, lone pair repulsions and pi-complex formation to proposals such as the unsupported pi-bond model and the sigma-bridged-pi bond concept. It is pointed out that a unified description based on a combination of closed and open 3-centre 2-electron bonds is possible. The role of hybridisation is emphasized in the short phantom bond computed in an earlier model system. These insights are used to predict structures with exceptionally short Si..Si and B..B phantom bonds. The proposals are confirmed by ab initio calculations.

First-order hyperpolarizabilities and pKa of weak organic acids in protic solvents are lineraly related

Second-order nonlinearities (beta) of five weak organic acids in protic solvents have been measured by the double-quantum Rayleigh scattering (DRS) technique. beta is found to bear a linear relationship to the pK(a) of these compounds in those solvents. A direct implication of this observation is that the DRS technique can be used to determine the pK(a) of weak organic acids in any solvent.

Dissociation constants of weak organic acids in protic solvents obtained from their first hyperpolarizabilities in solution

The first hyperpolarizabilities (beta) of some weak aromatic organic acids have been measured in protic solvents by the hyper-Rayleigh scattering (HRS) technique at low concentrations. The measured hyperpolarizability (beta(m)) varies between the two extreme limits: the hyperpolarizability of the acid form (beta(HA)) at the lower side and that of the basic form (beta(A-)) at the higher side. The degree of dissociation (alpha) of the acid in a solvent is related to the measured hyperpolarizability, beta(m), by the following relationship: beta(m)(2)=(1-alpha)beta(HA)(2)+alpha beta(A-)(2). The calculated beta's including solvent effects in terms of an Onsager field do not reproduce the experimentally measured hyperpolarizabilities. Other solvent-induced effects like hydrogen bonding and van der Waals interactions seem to influence the first hyperpolarizability and, thus, indirectly the extent of dissociation of these weak acids in these protic solvents.